Composition of matter and method of producing



Patented Oct. 5, 1937 PATENT OFFICE COMPOSITION OF Mama AND, METHOD OF monucmc Irvin W. Humphrey, Wilmington, Dei., asslgnor to Hercules Powder C'ompany,

M, a corporation of Delaware No Drawing. Application November 28, 1932, Serial No. 644,885

19Claims.

This invention relates to a new composition of matter and method for its production. The new composition of matter contemplated by this invention comprises more particularly a reaction product formed by the reaction of a terpenealcohol containing a tertiary hydroxyl group with maleic anhydride. 'I'hereaction, for example, is believed to be in effect a condensation of a terpene alcohol containing a tertiary hydroxyl group and o maleic anhydride, reaction occurring at their double bonds.

The new compositionof matter contemplated by this invention will comprise essentially a condensation product of a terpene alcohol contain- [5 ing a tertiary hydroxyl group and maleic anhydride. The new composition, it is believed, will 7 have the empirical formula CuHraOz.

The new composition contemplated by this invention in crude form will be resinous, but may go be readily purified, as, for example, by steam distillation, or by distillation under reduced pressure, and after purification will be found to be a white, waxy solid with crystalline properties. The new composition may be found to be of an 55 acidic character, to have a saponification number of about 430-460 and to be capable of reacting with alcohols, such as methyl, ethyl, butyl, propyl, amyl, abietyl, stearol, ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol mono- 30 methyl ether, benzyl, glycerol, etc. Modifying agents may be added such as rosin, hydrogenated rosin, stearlc acid, succinic acid, 'oleic, sebasic acid, phthalic acid, drying oils, as linseed oil or China-wood oil or their fatty acids, etc., for the 35 production of resinous products variously adaptable for use in the commercial arts.

In the practical adaptation of the method in accordance with this invention, the terpene alcohol containing a tertiary hydroxyl group, will be 40 desirably reacted with maleic anhydride in about molar proportions, though it will be understood that an excess of either the terpene alcohol or Y the maleic anhydride may be used, the excess being recovered after completion of the reaction.

45 The reaction will be preferably effected in the presence of heat and may be effected in the presence of a suitable catalyst. If desired, the reaction may be carried out in the presence of a suitable agent, which will assist in the removal of water 50 of reaction, the formation of water being one of the steps in the condensation reaction.

In the practical adaptation of this invention, the terpene alcohol containing a tertiary, hydroxyl group may be, for example, a terpineol, as

55 alpha-terpineol, a terpin, beta-terpineol, gammaterpineol, terpinenol-l, terpinenol-4, etc., or other reactive tertiary terpene alcohol. Further, the terpene alcohol may be technical terpineol or as present in pine oil or in certain essential oils.

In carrying out the method for the production of the new composition'maleic anhydride as such may be used or equivalently, one may use maleic or fumaric acid, which'under the proper reaction conditions will be converted into maleic anhydride for reaction with the terpene alcohol;

A suitable catalyst may on occasions be used for promoting the reaction, though it will be understood that the use of a catalyst is generally unnecessary and may even be' undesirable. If a catalyst is used such may be, for example, zinc chloride, aluminum chloride, p-toluene sulphonic acid, etc.,' may be used. Where it is desired to use an agent to aid in the removal of water of reaction, for example, xylene or toluene may be used.

In carrying out the method the terpene alcohol and maleic anhydride will be reacted in molar proportions, though, as has been indicated, excess of either of the reactants may be used, excess being recovered on completion of the reaction. The reaction will desirably be carried out in the presence of heat say,.for example, at a temperature within about the range 100-200 0; Where a catalyst is used, such may be used in amount within the range say about 1-5% of the amount of maleic anhydride employed. Where an agent is used to aid in removal of water of reaction, such may be used in any suitable amount. It will be understood, of course, that particular temperatures and proportions of reactants, amount of agent aiding in the elimination of. water of reaction, etc., are not of the essence of this invention, but will be dictated by good'practice. As

illustrative of the carrying out of the method in accordance with this invention for the production of the new composition with the use of,-for example, alpha-terpineol as the terpene alcohol, one

may proceed as follows: I

About 154 parts of alpha-terpineol and 98 parts of maleic anhydrlde are heated together at a temperature of 125-l35 C. for three to four hours. 'At the end of the heating period the volatile portions of the reaction mixture may be removed by steam distillation and the nonaqueous residue dried if desired. The drying of the non-aqueous residue may be accomplished by suitable heating or with the use of calcium chloride, sodium sulphate, or the like. The crude product, thiocyanate value 2.3, obtained may be refined for the obtaining of a very fl t colored product in the nature of a waxy solid having crystalline properties by partially distilling the treated residue at a temperature of about 140-150 C.

under pressure oi about 1-2 mm. Hg. I II If desired, in following the procedure of this example, xylene may be used in the amount of about 150 parts to aid in the removal of water.

As a further illustration of the carrying out of the method of this invention, for example, a mix. ture of about parts of terpin, 29 parts of maleic anhydride and 50 parts of xylene is distilled in such manner as to remove the water formed in the reaction and return the non-aqueous material to the reaction mass. When the reaction is complete the volatile materials are removed by distillation with steam and the non-aqueous ture 01' about 110-120 C. and then for several A hours at a temperature of about 150-175 C. The terpineol contained in the pine "oil will condense with the maleic anhydride, while most of the secondary alcohols, as borneoland i'e ehyl alcohol, will form acid maleates. I Oncomp etionof the I reaction the non-reactive pine oil components alpha-terpineol, as a cut may be removed by distillation under reduced pressure or by direct steam distillation. The product will be'a sott resinous acidic product which may be esterified with alcohols with or without a modifying agent. Likewise, if desired, one may use, for example, a pine'oil cut rich in boiling, for example, at 215-220 C.

In the reaction or maleic anhydride with pine oil the maleic anhydride will react with the alphaterpineol oi' the pine oil and with certain other tertiary alcohols which may be present to form a resinous product. The maleic anhydride will react with the secondary alcohols, as borneol and tenchyl alcohol, which are present to form acid maleates, the reaction with the secondary alcohols being partialor complete depending upon the temperature employed, proportion of maleic anhydride, etc.

It will be appreciated that from the broad standpoint this invention contemplates from the product standpoint the composition resultant from the reaction 01' a terpene alcohol and maleic anhydride and contemplates from the method standpoint the reaction of a terpene alcohol and maleic anhydride.

It will be understood that in detailing practical procedure by way 01' illustrating the carrying outsof the method in accordance with this invention, it is not intended that the details given shall" restrict the invention from either the process orthe product-standpoint. It will be appreelated that various modifications. oi the method and product outlined, herein for illustrative purposes may be made without departing from the scope of theinvention.

It will be, understood that in proceeding in accordance with this invention maleic acid or fumaric acid or mixtures thereof may be used in I some instances equivalently ior maleic anhydride.

, What I claim and desire to protect by Letters Patent is:

1. The method for producing a new composition of matter which includes eacting components consisting of a terpene al ohol containing a tertiary hydroxyl group and maleic anhydride I in the presence of a catalyst selected from the' group consisting of zinc chloride, aluminum} chloride and, p-toluene sultonic acid.

2. The methodior producing a new composition of matter which includes reacting components consisting of a terpene alcohol containing a tertiary hydroxyl group and maleic anhydride in the presence of heat and a catalyst selected from the group consisting of zinc chloride, aluminum chloride and 'p-toluene sulionic acid.

3. The method for producing a new' composition of matter which includes reacting components consisting of alpha-terpineol and maleic anhydride in the presence of heat and a catalyst selected from the group consisting of zinc chloride, aluminum chloride and p-toluene sulphonic acid.

4. A synthetic resin formed by the reaction of an alcohol with the condensation product oi maleic anhydride and a terpene alcohol containing a tertiary hydroxyl group.

5. A synthetic resin formed by thereaction of a polyhydric alcohol with the condensation product of maleic anhydride and a terpene alco-.

an alcohol with the condensation product of maleic anhydride and alpha-terpineol.

8. A synthetic resin formed by the reaction of a polyhydric alcohol with-the condensation product 01' maleic anhydride and alpha-terpineol.

9. The method of producing a synthetic resin i which comprises first reacting components consisting of maleic anhydride and a terpene alcohol containing a tertiary hydroxyl group, and then reacting the condensation product so formed with an alcohol. v

10. The method oi producing a. synthetic resin which comprises first reacting components consisting of maleic anhydride and a terpene alcohol containing a tertiary hydroxyl group, and

then reacting the condensation product so iorme'd with a polyhydric alcohol.

11. 'Asynthetic resin formed by the reaction of an aliphatic alcohol with the condensationproduct otmaleic anhydride and a terpene alcohol containing a tertiary hydroxyl group.

12. A synthetic resin fol-med by the reaction of an aliphatic glycol with the condensation product 01 maleic anhydride. and a terpene alcohol contalning a tertiary hydroxyl group. I

13. A synthetic resin formed by the reactiono ethylene glycol with the condensation product 01 maleic anhydride and a terpenealcohol containing a tertiary hydroxyl group. I

I 14. A synthetic resin formed 'by the reaction of glycerol with the condensation product of taing a tertiary hydroxyl group.- I

15. A synthetic resin formed by the reaction -maleic anhydride and a terpene alcohol con-, 7

of an aliphatic alcohol with the condensation product of maleic anhydride and alpha terpineol. 16. A synthetic .resin. formed by the reaction of an aliphatic glycol with the condensation productoi. maleic anhydride and alpha terpineol.

1'7. A synthetic resin formed by the reaction of the condensation product of maleic anhydride 0! an ethylene glycol with the condensation-prodand a terpene alcohol containing a tertiary hyuct of maleic anhydride and alpha terpineol, drox'yl group with an aliphatic polyhydric alcohol 18. A synthetic resin formed by the reaction and a modifying agent selected from the group of a glycerol with the condensation product or consisting of organic acids, natural resins and 5 maleic anhydride and alpha terpineol. glyceride oils. 7

19..A synthetic resin to'rmedby the reaction IRVIN W. HUMPHREY. 

